Addition-type copolymers having extralinear glycidyl and amino groups and process for their preparation



United States Patent ADDITION-TYPE COPGLYMERS HAVING EXTRA- LINEARGLYCIDYL AND AMINO GROUPS AND PROCESS FOR THEIR PREPARATION HenryShirley Rothrock and Charles William Tullock,

Wilmington, Del., assignors to E. I. du Pont de Nemours and Company,Wilmington, Del., a corporation of Delaware No Drawing. ApplicationApril 1, 1955 Serial No. 498,766

Claims. (Cl. 2 .50-86.11)

This invention relates to new polymers and their preparation, and, moreparticualrly, to soluble addition-type polymers containing extralinearglycidyl and amino groups adapted to be crosslinked upon heating and toa process for preparing these polymers.

This application is a continuation-in-part of applicants Serial No.415,681, filed March 11, 1954, now abandoned.

It has recently been found that partial amination of linear polymerscontaining extralinear oxirane groups produces products which arevaluable as coating and impregnating compositions for metals, wood,textiles, paper, etc., as adhesives, dispersing agents for waxes andoils, as binders for printing inks and paints, and in many otherapplications. These products are linear polymers containing extralinearoxirane groups, hydroxyl groups and extralinear primary, secondary ortertiary amino groups. They have been prepared by reacting a linearpolymer bearing extralinear oxirane groups with ammonia or a primary orsecondary amine in amount insufficient to react with all the oxiranegroups, whereby a portion of the latter is converted to hydroxyl andamino groups, as illustrated by the scheme.

where R and R are hydrogen or organic radicals.

The preparation of polymers containing both oxirane and amino groups byamination of a preformed oxiranecontaining polymer is not free fromdisadvantages. Polymers so obtained necessarily have as many hydroxylgroups as amino groups when there is no crosslinking, and the number ofhydroxyl groups is further increased if crosslinking occurs, as ahydroxyl group is formed along with each crosslink. Such a large numberof hydroxyl groups increases the Water sensitivity and is undesirablefor many uses, as when maximum resistance to water sensitivity isrequired in coating. The method requires two separate steps, viz.,polymerization of the unsaturated oxirane monomer, followed byamination. The latter step must be carefully controlled in order toproduce the desired degree of amination while avoiding prematurecrosslinking of the residual oxirane groups with the amino groups formedin the polymer.

An object of the present invention is to provide a new class of soluble,linear, i.e., non-crosslinked polymers which may be crosslinked readilyto an insoluble condition. A further object of the invention is toprovide a direct and economical process for preparing these solublepolymers from monomers. Other objects will become apparent from thedescription of the invention given hereinafter and the claims.

The above objects are accomplished according to the present invention byheating together in a homogeneous, one-phase system in the presence ofan azo polymerization initiator at a temperature below about 120 (3., apolymerizable mixture, the polymerizable ingredients of which are allmonoethylenically unsaturated compounds and comprise, by total weight ofsaid polymerizable ingredients, from 0.5% to 99% of a compound having aterminal glycidyl group attached to a terminal methylene group throughan aliphatic group of one to three carbon atoms containing an oxygenlinkage (ether or ester) in the chain. connecting the terminal groups,and from 0.5% to 99% of a monoethylenically unsaturated monoamine havinga basicity expressed by a pK base value below 6.0. The invention furthercomprises, as a new class of soluble addition-type copolymers composedof substituted hydrocarbon chains, free of hydroxyl groups and adaptedto be crosslinked to an insoluble condition upon heating, thecopolymerization products of a terminal glycidyl group-containingcompound of the class specified above and of a polymerizable aminehaving a basicity expressed by a pK base value below 6.0.

According to this invention, the polymerizable mixture contains twoessential polymerizable ingredients, one of which is a monoethylenicallyunsaturated compound of the class described containing a terminalglycidyl group, and the other of which is a monoethylenicallyunsaturated monoamine having a pK base value below 6.0. It has beenfound, despite the fact that the monoamine in the polymerizable mixtureis one of strong basicity, that the mixture can be polymerized, in ahomogeneous, one-phase system at a temperature below about C. in thepresence of one of the well-known class of azo polymerizationinitiators, to give a soluble, linear copolymer, that is, a copolymercomposed of substituted hydrocarbon chains in which there has been noappreciable reaction between the glycidyl and amino extralinear groups.

The copolymers prepared according to the present invention are readilycrosslinked, owing to the strong basicity of the monoamine component.Thus, these copolymers are well adapted to the formation of waterandorganic solvent-resistant films and coatings.

The crosslinking referred to above results from the interaction betweenthe glycidyl groups and the amino groups present in the copolymers, thisinteraction taking place when the copolymer is isolated and dried,especially upon heating at moderate temperatures, e.g., 50 to C. Thecrosslinking mechanism presumably takes place according to the followingscheme, where R is hydrogen or an organic radical, i.e., when primary orsecondary amino groups are involved:

With tertiary amino groups, formation of quaternary ammonium crosslinkspresumably takes place, in the 3 presence of added or atmospheric waterand/ or acid such as carbonic acid, as illustrated by the scheme t-la -Jwhere R is an organic radical and X is hydroxyl or an anion. Because ofthis crosslinking reaction, the copolymers prepared in accordance withthis invention, when air-dried and/ or baked at elevated temperatures,are converted to films or coatings which are insoluble in, or highlyresistant to water and organic solvents. It should be noted,.however,that prior to crosslinking, that is, when kept in solution in a suitablesolvent (e.g., an organic solvent or an aqueous acidic medium), thesecopolymers are quite stable and can be stored for long periods of time.Thus, they possess the great advantage of convenient handling andshipping without deterioration.

It will be apparent from the above discussion that the polymerizablemonoamines suitable for use in this invention can be primary, secondaryor tertiary. Many unsaturated monoamine compounds having acyclic aminonitrogen have been previously described and a number of them arespecifically referred to in the examples and discussion which follow. Apreferred class of monomers is represented by the formulaNCHz-CH2OR1=CH3 where R and R are hydrogen or alkyl radicals, R containsone to three carbon atoms and R =CH is a monoethylenically unsaturatedacyl group or alkenyl group.

The polymerizable glycidyl group-containing compounds suitable for usein this invention are those in which a terminal glycidyl group isattached by a carbonoxygen chain of atoms to a terminal vinylidene,including vinyl, group. A preferred class of monomers is repre sented bythe formula wherein R contains one to three carbon atoms and -R =CH is amonoethylenically unsaturated acyl group or alkenyl group, e.g.,acrylyl, methacrylyl, allyl, or methallyl radicals.

The invention is illustrated in greater detail in the followingexamples, in which all proportions are by weight unless otherwisestated.

Example I A solution of 80 parts of glycidyl methacrylate and 20 partsof beta-diethylaminoethyl methacrylate in 440 parts of benzenecontaining 0.5 part of alpha,alpha'-azobis(alpha,gamma-dimethylvaleronitrile) was heated at 49 C.-59 C. withstirring in a nitrogen atmosphere for six hours. Addition of thereaction mixture to diethyl ether caused precipitation of the glycidylmethacrylate/ beta-diethylaminoethyl methacrylate copolymer, which wasredissolved in benzene and reprecipitated in petroleum ether. Thecopolymer was redissolved in dioxane and kept in solution in thatsolvent. Evaporation of an aliquot of the dioxane solution indicated at69% yield of copolymer. The dry material contained 1.56% nitrogen,corresponding to 20.5% of polymerized beta-diethylaminoethylmethacrylate. A test portion of the freshly precipitated polymer wasreadily soluble in aqueous acetic acid. 7 I I A dioxane solution of thiscopolymer of about 15% concentration was completely stable after storingat room temperature for five months. In contrast, the solid polymerafter standing at room temperature for seven days was no longer solublein dioxane or acetone.

A film of this copolymer was insolubilized by heating at 102 C. forthirty minutes or at 145 C. for 22 minutes to yield a' clear, hardcomposition. Similarly, films cast from aqueous acetic acid and heatedat 102 C. to 117 C. for thirty minutes were clear and insoluble. I

Example II A solution of 18.5 parts of beta-diethylaminoethylmethacrylate and 14.2 parts of glycidyl methacrylate in 175 parts ofbenzene containing 0.17 part of alpha,alpha'-azobis(alpha,gamma-dimethylvaleronitrile) was heated at 48 C. to 56 C.with stirring in a nitrogen atmosphere for four hours. The glycidylmethacrylate/beta-diethylaminoethyl methacrylate copolymer was isolatedby precipitation in petroleum ether and purified by redissolving it inbenzene and reprecipitating with petroleum ether. After" drying atreduced pressure and room temperature, there was obtained 20.6 parts(63% yield) of copolymer. This material contained 5.86% oxirane oxygen,corresponding to 52% by weight of polymerized glycidyl methacrylate. Thecopolymer was initially soluble in acetone, dioxane, benzene and 10%aqueous acetic acid, but it slowly became insoluble on standing in thesolid form at room temperature. Films of the copolymer wereinsolubilized by heating at C. for twenty minutes. Much harder filmswere obtained by heating at 150 C.

Example III Using essentially the procedure described in Example I, aglycidyl methacrylate/beta-diethylaminoethyl methacrylate copolymer wasprepared from 20 parts of glycidyl methacrylate and 80 parts ofbeta-diethylaminoethyl methacrylate. This copolymer contained 5.75%nitrogen, corresponding to 76% by weight of polymerizedbetadiethylaminoethyl methacrylate. was still stable after five monthsstorage at room temperature. On heating a film of this copolymer at C.for 22. minutes, there was obtained a moderately tough, clear, soft,extensible film which was insoluble in dioxane at room temperature,although it was swelled by it.

Example IV A solution of 14.2 parts of glycidyl methacrylate, 8.7 partsof beta-vinyloxyethylamine (B.P. 117 C. to 118 C.) (prepared bycondensing acetylene at 200 lb./sq. in. pressure and 110 C. withmonoethanolamine in the presence of potassium hydroxide catalyst) and0.12 part of alpha,alpha azobis(alpha,gamma-dimethylvaleronitrile) inparts of dioxane was heated at 53 C. for five hours in an agitatedpressure vessel. The glycidyl methacrylate/beta-vinyloxyethylaminecopolymer, obtained in 27.5% yield, was isolated by pouring the solutioninto diethyl ether and immediately redissolving the precipitated polymerin dioxane. Nitrogen analysis (0.95% nitrogen) of the dry product andneutralization equivalent of an aliquot of the solution showed that thematerial contained 5.9% by weight of polymerizedbeta-vinyloxyethylamine.

The freshly precipitated polymer was soluble in 10% aqueous acetic acidbut it became insoluble in that solvent after standing at roomtemperature for 25 minutes, indicating rapid crosslinking. Dioxanesolutions of the polymer remained clear for two days at room temperaturebefore developing an opalescence; small amounts of highly swollenpolymer separated from these solutions within three or four days.Solutions of the polymer in acetone containing sufiicient acetic acidfor neutralization remained stable for several weeks at roomtemperature.

Films prepared by casting dioxane solutions of the polymer at roomtemperature became insoluble as soon.

Its dioxane solution as the dioxane' had evaporated, e.g., within 30 to60 minutes. These films were unaffected by dioxane, ethanol or benzeneat room temperature. They were softened but not spotted by warm water,and they were only softened by aqueous potassium hydroxide and 10%hydrochloric acid at room temperature in 30 minutes. However, films castfrom an acetone solution of the polymer neutralized with acetic acid didnot crosslink with the same rapidity. Heat curing, e.g., at 158 C. for10 minutes, was required to insolubilize these films.

Example V An allyl glycidyl ether/beta-diethylaminoethyl methacrylatecopolymer was prepared by slowly adding a solution of 25 parts ofbeta-diethylaminoethyl methacrylate, 58.5 parts of allyl glycidyl etherand 2 parts of 1,1- azodicyclohexane carbonitrile over a period of 1.3hours to 117.5 parts of allyl glycidyl ether containing 2 parts of1,1-azodicyclohexane carbonitrile and heated at 103 to 110 C. Afteraddition was completed, the reaction mixture was heated for 1.5 morehours at 110 C. Upon removal of the excess allyl glycidyl ether byWarming under reduced pressure, there remained 48.7 parts of thecopolymer as a clear, brown, viscous syrup. This material contained 3.8%nitrogen, corresponding to 50% by weight of polymerizedbeta-diethylaminoethyl methacrylate. Dioxane solutions of the polymerwere stable at room temperature but the polymer itself became insolubleafter standing at room temperature for two days. Films of the polymercrosslinked on heating at 145 C. for 30 minutes to give clear, softfilms insoluble in organic solvents.

Example VI A solution of 49 parts of beta-dimethylaminoethylmethacrylate and 1 part of glycidyl methacrylate in 258 parts of dioxanecontaining 0.1 part ofalpha,alphaazobis(alpha,gamma-dimethylvaleronitrile) was heated at 52 C.for six hours in a nitrogen atmosphere in an agitated pressure vessel.The beta-dimethylaminoethyl methacrylate/glycidyl methacrylatecopolymer, obtained in 34% yield, was isolated by adding the solution topetroleum ether, redissolving the polymer in dioxane and reprecipitatingit by addition of petroleum ether. Nitrogen analysis of the dry product(8.42% nitrogen) showed that the polymer contained 95% by weight ofpolymerized beta-dimethylaminoethyl methacrylate. On heating a film ofthis polymer at 130 C. for 25 minutes, there was obtained a tough, clearfilm swellable by water but insoluble in dioxane. This polymer, whenapplied to fabrics of polyhexamethylene adipamide, polyethyleneterephthalate, and polyacrylonitrile, and cured by heating at 130 C. for30 minutes, followed by washing in 0.5%

soap solution at 65 to 70 C. for 2%. hours, was found to contribute goodantistatic properties, as judged by conductivity measurements of thefabrics to an electric current.

Example VII A solution of 10 parts of glycidyl methacrylate, 90 parts ofbeta-diethylaminoethyl methacrylate and'O.5 part ofalpha,alpha-azodiisobutyronitrile in 500 parts of dioxane was evenlydivided among four pressure bottles which were flushed with nitrogen,capped and heated at 75 C. for six hours in a rotating cage immersed ina water bath. Dioxane and unreacted monomers were removed for the mostpart by warming at 60 to 65 C. under to mm. pressure, followed bywarming at 100 C. under the same pressure. The polymer was purified bydissolving it in 70 parts of diethyl ether and pouring this solutioninto 400 parts of petroleum ether. The polymer, Which solidified oncooling in a carbon dioxide/acetone bath, was redissolved in diethylether and precipitated a second time. The remaining polymer wasdissolved in dioxane. Evaporation of a test portion of this solutionshowed that it contained 81 parts of a glycidylmethacrylate/betadiethylaminoethyl methacrylate copolymer, which wasfound by oxirane oxygen determination to contain 3.2% by weight ofpolymerized glycidyl methacrylate. This copolymer crosslinked readily,either by heating at 132 C. for 30 minutes or by heating with a trace ofphosphoric acid at 115 C. for forty minutes, to give a polymer which wasno longer soluble in dioxane.

Example VIII A solution of 175 parts of allyl glycidyl ether, 75 partsof .beta-diethylaminoethyl methacrylate and 2.5 parts ofalpha,alpha'-azodiisobutyronitrile in 250 parts of dioxane Was evenlydivided among four pressure bottles, which were flushed with nitrogen,capped and rotated in a water bath at 70 C. for twenty-two hours. Thelight brown colored solution was concentrated by Warming at C. and 18 to20 mm. pressure to remove the dioxane, then at 2 to 4 mm. pressure toremove unreacted monomers. The sticky viscous polymer left was dissolvedin 125 parts of diethyl ether and precipitated by adding this solutionslowly with stirring to 600 parts of petroleum ether. The polymer waspurified once more in a similar manner, then dissolved in dioxane.Evaporation of a test portion of this solution showed that it contained79.6 grams of an allyl glycidyl ether/beta-diethylaminoethylmethacrylate copolymer, which was found by oxirane oxygen determinationto contain 3.2% of polymerized allyl glycidyl ether. This copolymercrosslinked readily, either by heating at 144 C. for thirty minutes orby heating with a trace of phosphoric acid at C. for fifteen minutes, togive a polymer which was no longer soluble in dioxane.

It will be understood that the above examples are merely illustrativeand that the present invention broadly comprises the preparation ofsoluble addition-type copolymers,- adapted to be crosslinked uponheating, by polymerization of a polymerizable mixture containing, asessential ingredients, (1) a polymerizable compound having a terminalglycidyl group attached to a terminal methylene group through analiphatic group of one to three carbon atoms containing an oxygenlinkage in the chain connecting the terminal groups, and (2) apolymerizable monoethylenically unsaturated monoamine having a basicityexpressed by a pK base value below 6.0, and, as a new class ofcopolymers, those copolymers thus prepared which are free of hydroxylgroups. Suitable glycidyl monomers of the above class include glycidylmethacrylate, glycidyl acrylate, allyl glycidyl ether and Z-methallylglycidyl ether.

It should be noted that the monomers of this class which contain aterminal glycidyl group, are far more suitable for the preparation ofcrosslinkable copolymers with unsaturated, strongly basic amines thanare monomers in which the 1,2-epoxy group is internal rather thanterminal. This much greater reactivity of the terminal 1,2epoxy groupcan be shown, for example, by comparing the copolymers of Examples V111and VIII with a copolymer prepared in essentially the same manner fromthe same unsaturated amine, viz., beta-diethylaminoethyl methacrylate,but from an epoxy monomer in which the 1,2-epoxy group is internal,viz., 4-vinylcyclohexene monoepoxide. At substantially the same contentof polymerized epoxy monomer, it is found that the copolymers ofExamples VII and VIII are superior to the 4-vinylcyclohexenemonoepoxide/beta-diethylaminoethyl methacrylate copolymer from the veryimportant standpoints of ease of thermal crosslinking, ease ofacidcatalyzed crosslinking and resistance of the crosslinked polymers tosolvents, acids and alkali.

The polymerizable monoethylenically unsaturated monoamines of pK basevalue below 6.0 suitable for use in this invention include thebeta-dimethylaminoethyl and beta-diethylaminoethyl esters of acrylic andmethacrylic acids, and beta-vinyloxyethylamine. These monoamines, forexample, beta-dimethylaminoethyl methacrylate (pK base value 5.74);beta-diethylaminoethyl methacrylate (pK base value 5.16); andbeta-vinyloxyethylamine (pK base value 4.85) are strongly basic. Suchmonoamines react much more readily than weak monoamines do with theoxirane groups in the polymer to form a crosslinked polymer. Theseamines are aliphatic or acylic, that is, the amino nitrogen is acyclic,i.e., not a member of a cyclic structure. In comparison, cyclicmonoamines of aromatic character are usually weakly basic, e.g.,2-vinylpyridine has a pK base value of 9.48. The proportion of the twoessential components of these copolymers can be varied greatly but eachshould be present in an amount suflicient to give a copolymer which willcrosslink on heating. Actually, copolymers containing 0.5% or even less,by combined weight of the two essential components, of either thepolymerizable glycidyl compound or the polymerizable monoamine, willcross-link on heating. Preferably, the copolymer will contain at least1% by weight of each essential component, that is, in a polymerprimarily consisting of the two essential components, from about 1% toabout 99% of each component. Still more preferred, because of thegreater flexibility of the resulting films, are the copolymerscontaining between about 1% and 50%, by weight. of the polymerizedglycidyl group-containing monomer. Such copolymers will readilycrosslink to give products well adapted for the formation of water-andorganic solvent-resistant films and coatings.

In preparing these copolymers, the proportion of the essentialingredients in the mixture of polymerizable ingredients likewise can bevaried greatly. For example, from 1% to 99% each of the polymerizablecompound containing the glycidyl group and the polymerizable monoaminecan be used. As the examples illustrate, it is preferred to use about 2%to 90% of the glycidyl compound and 98% to 10% of the monoamine. Due tothe difierent rates of polymerization of specific compounds, theproportion of each ingredient in the polymerizable mixture may varyappreciably from the proportion of that ingredient in the copolymer.

The copolymers of this invention are addition-type copolymers ascontrasted to condensation-type copolymers and the instant processinvolves free radicalinitiated polymerization. T o obtain a solublecopolymer, i.e., one that is substantially free of crosslinking, it hasbeen found that the type of free radical initiator used is apparently acritical factor. For example, the commonly used organic peroxideinitiators are not suitable because they lead to premature crosslinkingand/or other undesirable side reactions. So far as has been determined,the class of azo polymerization initiators is the only one suitable foruse in the process of this invention. These azo polymerization catalystsare now well known in the art and they are disclosed in great detail inUS. Patent No. 2,471,959 to Hunt. 7

Any specific member of the class of azo polymerization initiators can beused in this invention. The azonitriles such asalpha,alpha-azodiisobutyronitrile; alpha,alpha'- azobis(alpha,garnmadimethylvaleronitrile); dimethylalpha,alphaazodiisobutyrate;1,1-azodicyclohexanecarbonitrile; and the like, are particularlysuitable for use in this process. The initiator need be used only inminor amounts, e.g., between 0.1% and based on the total weight ofpolymerizable materials.

The polymerization should be carried out in a homogeneous, one-phase,fluid system since, if the resulting copolymer is not maintained insolution, premature crosslinking may take place. It is not essential touse an extraneous solvent as one or more of the polymerizable componentscan act as solvent for the polymer, particu- July when thepolymerization is interrupted before it is completed or far advanced.However, the use of an unpolymerizable organic solvent is generallydesirable. For this purpose, it is preferred to use inert solvents,including aromatic hydrocarbons such as benzene, toluene, or the 8xylenes; ketones such as acetone, methyl ethyl ketone, methyl isobutylketone, or cyclohexanone; ethers having active solvent power such asdi-n-butyl ether or dioxane; and the like. Other solvents which cannotbe viewed as completely inert can be used, for example, alcohols such asethanol, isopropyl alcohol, n-butyl alcohol or tertiary butyl alcohol.Solvents which are active chain-transfer agents such as isopropylalcohol tend to lower the molecular weight of the copolymer produced andhave special usefulness when this is desired. The amount of solvent,when one is used, is not critical and can vary within wide limits, forexample, between 10% and 1000%, preferably between 50% and 500%, of thetotal weight of the monomers. Mixtures of solvents can be used ifdesired.

The polymerization temperature should not exceed about C., as otherwisethe danger of premature crosslinking of the polymer is too great. Thereis no critical lower limit on the temperature range, as somepolymerization will take place at room temperature (about 20 C.) or evenlower. To attain a practical speed of reaction, a temperature above 40C. will normally be used, and a range of 50 C. to 120 C. is preferred.Atmospheric pressures are conveniently used, for example, in openvessels provided with a reflux condenser, but the reaction can also becarried out in closed vessels under the autogenous pressure of thereactants, and additional pressure can be applied if desired.

The copolymers can be isolated by various means, for example, simply byevaporating the unchanged monomers and solvent, if any, under reducedpressure, or by pouring the fluid reaction mixture into a non-solventforthe polymer. The polymer can be purified by redissolving it in anappropriate solvent and reprecipitating it in a non-solvent.

As has been shown, the copolymers obtainable by the process of thisinvention are particularly valuable in coating compositions because oftheir ability to crosslink rapidly to yield insoluble, resistantmaterials. This insolubilization mechanism does not depend on external,uncontrollable factors such as air-oxidation, but upon the internalstructure of the copolymers. The copolymers are therefore useful asclear finishes for metals, wood, glass, ceramics, textiles, paper andother substrates and may be used either as primer-sealer coats forsubsequent application of other finishes or as the total protective ordecorative finish for these substrates. In addition to clearcompositions, pigmented coating compositions are readily prepared byincorporating in the copolymer a wide variety of commonly used pigments,such as titanium dioxide, carbon black, iron blues, phthalocyanine bluesand greens, metal oxides and chromates, organic maroons and variousinert extenders such as talc, barytes and china clay. Other film-formingmaterials compatible with the copolymers and soluble in the samesolvents may be blended with them to produce clear or pigmentedcompositions, including urea-formaldehyde resins, melamineformaldehyderesins, alkyd resins and other natural and synthetic polymers. Thecopolymers obtainable by the process of this invention are furtheruseful as pigment dispersing agents, pigment binders in the preparationof water paints and pigment printing compositions, and antistatic agentsfor natural or synthetic fabrics.

As many apparently widely difterent embodiments of this invention may bemade without departing from the spirit and scope thereof, it is to beunderstood that the invention is not limited to the specific embodimentsthereof except as defined in the appended claims.

What is claimed is: v

1. A soluble linear copolymer composed of hydrocarbon chains having, asessential extralinear substituents, glycidyl-terminating andmonoaminoalkoxy-terminating groups, any other oxygen-containingextralinear substituent being aliphatic and terminating in an alkylgroup, said copolymer being converted to an insoluble crosslinkedpolymer by reaction of said glycidyl groups with said monoaminoalkoxygroups upon heating to 50 to 150 C., and wherein said copolymer consistsof a polymerized mixture of 1% to 99% of a compound selected from thegroup consisting of the glycidyl ethers of allyl and methallyl alcoholsand the glycidyl esters of acrylic and methacrylic acids, 1% to 99% of acompound selected from the group consisting of thebeta-diethylaminoethyl and beta-dimethylaminoethyl esters of acrylic andmethacrylic acids and beta-vinyloxyethylamine.

2. A copolymer as defined in claim 1 in which the monoamine monomer isbeta-diethylarninoethyl methacrylate and the glycidyl group-containingmonomer is glycidyl methacrylate.

3. The process for preparing a soluble addition-type copolymer, free ofhydroxyl groups and adapted to be crosslinked to an insoluble conditionon heating, which comprises heating together in a homogeneous, one-phasesystem in the presence of an azo polymerization initiator at atemperature below about 120 C., a polymerizable mixture ofmonoethylenically unsaturated compounds consisting of 0.5 to 99% of acompound selected from the group consisting of the glycidyl ethers ofallyl and methallyl alcohols and the glycidyl esters of acrylic andmethacrylic acids, 0.5 to 99% of a compound selected from the groupconsisting of the betadiethylaminoethyl and beta-dimethylaminoethylesters of acrylic and methacrylic acids and beta-vinyloxyethylamine. t 1

4. Process as set forth in claim 3 wherein said liquid inert organicsolvent is a liquid aromatic hydrocarbon and is present in an amountequal to about to of the total weight of the polymerizable ingredients.

5. Process of preparing a soluble addition-type copolymer adapted to becrosslinked upon heating, which comprises polymerizing in a liquid inertorganic solvent in the presence of an azonitrile polymerizationinitiator at a temperature of 50 C. to C. a polymerizable mixture, thepolymerizable ingredients of which consist of, by total weight of saidpolymerizable ingredients, from 2% to 90% of a compound from the groupconsisting of the glycidyl ethers of allyl and methallyl alcohols andthe glycidyl esters of acrylic and methacrylic acids, and from 98% to10% of a compound from the group consisting of thebeta-diethylaminoethyl and beta-dimethylaminoethyl esters of acrylic andmethacrylic acids and beta-vinyloxyethylamine.

References Cited in the file of this patent UNITED STATES PATENTS2,138,763 Graves Nov. 29, 1938 2,604,463 Bilton et al. July 22, 19522,687,404 Robertson Aug. 24, 1954 2,737,496 Catlin Mar. 6, 19562,781,335 Cupery Feb. 12, 1957

1. A SOLUBLE LINEAR COPOLYMER COMPOSED OF HYDROCARBON CHAINS HAVING ASESSENTIAL EXTRANLINEAR SUBSTITUENTS, GLYCIDYL-TERMINATING ANDMONOAMINOALKOXY-TERMINATING GROUPS, ANY OTHER OXYGEN-CONTAININGEXTRALINEAR SUBSTITUENT BEING ALIPHATIC AND TERMINATING IN AN ALKYLGROUP, SAID COPOLYMER BEING CONVERTED TO AN INSOLUBLE CROSSLINKEDPOLYMER BY REACTION OF SAID GLYCIDY GROUPS WITH SAID MONOAMINOALKOXYGROUPS UPON HEATING TO 50* TO 150*C. AND WHEREIN SAID COPOLYMER CONSISTSOF A POLYMERIZED MIXTURE OF 1% TO 99% OF A COMPOUND SELECTED FROM THEGROUP CONSISTING OF THE GLYCIDY ETHERS OF ALLYL AND METHALLYL ALCOHOLSAND THE GLYCIDYL ESTERS OF ACRYLIC AND METHACRYLIC ACIDS, 1% TO 99% OF ACOMPOUND SELECTED FROM THE GROUP CONSISTING OF THEBETA-DIETHYLAMINOETHYL AND BETA-DIMETHYLAMINOETHYL ESTERS OF ACRYLIC ANDMETHACRYLIC ACIDS AND BETA-VINYLOXYETHYLAMINE.